DE2311638A1 - 4-TRIFLUOROMETHYL-4'-NITRODIPHENYL ETHER - Google Patents

Description

This invention relates to new compounds which have herbicidal activity, processes for the preparation of the new herbicidal compounds, compositions containing these new herbicidal compounds and methods of control from weeds with these new herbicidal agents.

It is known that certain diphenyl ethers are used as agents for Control of weeds are appropriate. The herbicidal effectiveness of a given diphenyl ether can from the Examination of the substituent groups attached to the phenyl rings of the ether are not predicted, so that very often closely related compounds have very different effects on weed control. Different diphenyl ethers can be overlapping or complementary Have ranges of activity or selectivity so that they are useful in combination for controlling a variety of weeds. The diphenyls previously known as herbicides * but ethers are not completely satisfactory. An ideal herbicide should have selective weed control throughout Growth period with a single application in low dosage. It should be able to do all the usual Control weeds by killing them as a seed, germinating seed, seedling, and growing plant. The herbicide should not be used against the others at the same time Crops are phytotoxic and should decompose or otherwise disappear in order to prevent the soil

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to poison ernd. The known diphenyl ethers correspond does not meet these ideal requirements, and there is therefore a desire to develop new herbicides that are more selective Show control of undesirable plants between the desired crops, or those that are known diphenyl ethers complement in their activity in a valuable way.

The subject of this invention is a new class of diphenyl ethers, which are particularly excellent herbicides and conform to the following formula:

in which X is a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, a trihalomethyl _{radical, preferably a trifluoromethyl radical, a (C 1} -C ^) alkyl radical, preferably a methyl radical or a cyano radical, Y is a hydrogen atom, a halogen atom, is preferably a fluorine atom or a chlorine atom, or a trihalomethyl radical, preferably a trifluoromethyl radical and
Z is a hydrogen atom, a hydroxyl group, an alkoxy group,

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preferably with 1 to 6 carbon atoms and particularly preferably with 1 to 4 carbon atoms, an alkyl radical, preferably with 1 to 4 carbon atoms, a halogen atom, preferably a chlorine atom or a fluorine atom, an amino group preferably with up to 6 carbon atoms, an alkylthio group, preferably with 1 up to 4 carbon atoms, a cyano radical, a carboxy group, a carbalkoxy group, -COoR, preferably with 1 to 4 carbon atoms in the alkoxy moiety, a carboxyalkyl group, -R ¹ COgH, preferably with up to 4 carbon atoms, a carbalkoxyalkyl group, -R ¹ COgR, preferred with up to 6 carbon atoms, an alkanoyloxy group, -OCOR, preferably with up to 4 carbon atoms, optionally substituted with a halogen atom, or a carbamoyloxy group, -OCONH ₂ »-OCONHR, or -OCONR ₂ , preferably with up to 6 carbon atoms.

In these definitions of the substituent Z, R means one Alkylrtft and R 'is a divalent alkylinreat, oils are alkyl or alkylene portions of the alkyl-containing substituents X and Z can either be straight-chain or branched or a possess cyclic spatial configuration.

The term "alkoxy group" used in the specification and in the claims includes both unsubstituted alkoxy groups and substituted alkoxy groups in which one or more of the hydrogen atoms has been replaced by a substituent. Among the substituted alkoxy groups that can represent the symbol Z, alkoxy groups with preferably up to 4 carbon atoms are »substituted with a halogen atom, a hydroxyl group, a (C ₁ -C ^) alkoxy group, a carboxy group, a carbalkoxy group, preferably with up to 4 Carbon atoms in the ester alkoxy group, a trihaloalkyl radical, preferably a trifluoromethyl radical, an alkenyl radical, an alkynyl radical, preferably an ethynyl radical, an amino group, an alkyl or dialkylamino group, including

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borrowed heterocyclic substituents such as morpholines », piperazino, Piperidino and the like. And preferably with a total of up to to 4 carbon atoms, an alkylthio group, preferably with up to 4 carbon atoms, an alkylsulfonyl group is preferred having up to 4 carbon atoms, an epoxy group, an alkylcarbonyl group including halo-substituted Alkylcarbonyl and preferably with up to 4 carbon atoms in the alkyl radical, very particularly preferably methylcarbonyl, a carbamoyl group including alkyl or dialkylcarbamoyl ,. preferably with a total of up to 4 carbon atoms in the alkyl substituents.

The term "amino group" used further includes one unsubstituted amino group, -NH ^, but also amino groups, in which one or both hydrogen atoms are substituted by substituents have been replaced, a. The substituted amino groups which may correspond to the symbol Z include Amino groups that are substituted with one or two alkyl radicals, preferably with a total of up to 6 carbon atoms, halo-, hydroxy- or alkoxy-substituted alkyl radicals, preferably with a total of up to 6 carbon atoms, one or two alkylthiocarbonyl groups, preferably with a total of up to 4 carbon atoms in the alkyl moiety, carboxy groups, carbalkoxy groups, preferably with up to 4 Carbon atoms in the alkoxy group, carbamoyl groups, including alkyl or dialkylcarbamoyl groups, preferably with up to 4 carbon atoms in the alkyl portion, Alkyl carbonyl groups, preferably with up to 4 carbon atoms or halo-substituted alkyl carbonyl groups, are preferred with up to 4 carbon atoms.

The substituted amino groups can also be heterocyclic amino groups, such as piperidino, piperazino, morpholino, Pyrrolidinyl and the like. When the substituent Z is a carboxyl group or contains a carboxy group, either the free acid or the salt form can be used.

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When Z is an alkyl group, it can optionally be substituted with one Hydroxy group, a (C -, - Ca) alkoxy group or a halogen atom, preferably a chlorine atom, may be substituted.

These new compounds are distinguished by an unexpectedly good effectiveness as a means for controlling weeds. In a preferred embodiment of the invention, X is a halogen atom or a cyano radical, Y is a hydrogen atom or a halogen atom and Z is an alkoxy group.

Specific examples of compounds according to the invention which correspond to formula I are:

alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether, 2-alpha, alpha, alpha-tetrafluoro-p-tolyl-4-nitrophenyl ether, 2-bromo-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether, 2-chloro-alpha, alpha, alpha-trifluor-p-tolyl-4-nitrophenyl ether, alpha, alpha, alpha-trifluoro-2-iodo-p-tolyl-4-nitrophenyl ether, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether,

2-chloro-6-alpha, alpha, alpha-tetrafluoro-p-tolyl-4-nitrophenyl ether,

2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether, 2-cyano ~ 6-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

• phenyl ether,

2-cyano-6, alpha, alpha, alpha-tetrafluoro-p-tolyl-4-nitrophenyl ether, alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro-2,4-xylyl-

4-nitrophenyl ether, 6-chloro-alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro-

2,4-xylyl-4-nitrophenyl ether,

alpha, alpha, alpha -trifluoro-2,4-xylyl-4-nitrophenyl ether, 2-butyl-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether, 2-chloro-6-ethyl-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

phenyl ether,

2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-m-tolyl ether,

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2-bromo-alpha, alpha-alpha-trifluor-p-tolyl-3-butyl-4-nitro-

phenyl ether,
2-τ alpha, alpha, alpha-Tetraf luor-p-tolyl ^ -nitro ^ -n-propoxy-

phenyl ether,
2-chloro-6, alpha, alpha, alpha-t etraf luor-p-tolyl-3-methylthio-

• 4-nitrophenyl ether,

2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-propyl-4-nitrophenyl ether,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-4-nitro-

diphenyl ether,
alpha, alpha, alpha-trifluoro-2-iodo-p-tolyl-3-ethoxy-4-nitro-

phenyl ether,
2,6-dichloro-alpha, alpha, alpha-trifluor-p-tolyl-4-nitro-3-n-

propoxyphenyl ether,
alpha, alpha, alpha, alpha ', alpha', alpha -hexafluoro-2,4-xylyl-

3-n-butoxy-4-nitrophenyl ether,
2-cyano-alpha _Ί alpha-, alpha-trifluor-p-tolyl-3-ethoxy-4-nitro-

phenyl ether,
2-chloro-6-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

3-n-propoxyphenyl ether,
2-cyano-alpha, alpha-, alpha _r trifluoro-p-tolyl-3-carboxy-4-nitro-

phenyl ether, 2,6-dibromo-alpha, alpha, alpha-trifluoro-p-tolyl-3-methoxy-

methoxy-4-nitrophenyl ether,
2-chloro-alpha, alpha, alpha-trifluor-p-tolyl-3- (2-hydroxyethoxy)

4-nitrophenyl ether,
2 _r alpha, alpha, alpha-tetrafluoro-p-tolyl-4-nitro-3-n-propyl-

aminophenyl ethers,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-dimethylamino-

4-nitrophenyl ether,
2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3-carbethoxy-4-

nitrophenyl ether,
2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-carbethoxy-

4-nitrophenyl ether,
2-ethyl-alpha, alpha, alpha-trifluoro-p-tolyl-3- (2-carboxyethoxy) ■

4-nitrophenyl ether,

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alpha, alpha, alpha _f alpha, alpha, alpha'-hexafluoro-2,4-xylyl-

3-carbethoxymethyl-4-nitrophenyl ether, 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl - $ - (2-carboxypropyl) -

4-nitrophenyl ether, Z- alpha, alpha, alpha-tetrafluoro-p-tolyl-3-carbäthoxymethoxy-

. 4-nitrophenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (3,3, -diethyl-

ureido) -4-nitrophenyl ether, 2-chloro-6-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetamido-

4-nitrophenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-carbäthoxyamino-

4-nitrophenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- J-

phenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-S-

phenyl ether, 2-bromo-alpha, alpha, alpha-trifluoro-p-tolyl-3-butynyloxy-4-

nitrophenyl ether, 2-cyano-alpha, alpha _r alpha-trifluoro-p-tolyl-3- (2-methyl) -

propynyJ.oxy-4-nitrophenyl ether, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (2,2,2 ₇

trifluoro) ethoxy-4-nitrophenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (2-dimethyl-

aminoethoxy) -4-nitrophenyl ether, 2-bromo-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy-4-nitro-

phenyl ether, alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro-2,4-xylyl-

3- (2-hydroxyäthylamino) -4-nitrophenyl ether, alpha, alpha, alpha -trifluoro-2,4-xylyl-3-amino-4-nitro-

phenyl ether, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-S-morpholine ^ -.

nitrophenyl ether _t 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3- (N-methylcarb-

amoyloxy) -4-nitrophenyl ether, 2-chloro-6, alpha, alpha, alpha-tetrafluoro-p-tolyl-3-propion-

amido-4-nitrophenyl ether,

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2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-chloroacetamido-

4-nitrophenyl ether,
alpha, alpha, alpha -trifluoro-2,4-xylyl-3- (2,3-epoxypropoxy) -

4-nitrophenyl ether,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (2,3-dihydroxy-

. propoxy) -4-nitrophenyl ether,
2-cyano-alpha, alpha, alpha-trifluor-p-tolyl-3- (2-methylthio-

ethoxy) -4-nitrophenyl ether _f
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (l-ethyl-3-

methylureido) -4-nitrophenyl ether, 2-bromo-alpha, alpha, alpha-trifluoro-p-tolyl-3- (2-methyl-

sulfonyiethoxy) -4-nitrophenyl ether, alpha, alpha, alpha, alpha, alpha, alpha '-Hexaf luor-2,4-xylyl-

3- (3-methylureido) -4-nitrophenyl ether, 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethylthiocarbonyl-

; amido-4-nitrophenyl ether,.

2-cyano-alpha, alpha, alpha-trifluor-p-tolyl-3-cyano-4-nitro-

phenylttther,
2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-carboxy-

4-nitrophenyl ether,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carbamoyl-

ethoxy) -4-nitrophenyl ether,
2-bromo-alpha, alpha, alpha-trifluor-p-tolyl-3- (3-oxobutoxy) -

. 4-nitrophenyl ether
and the like

The new diphenyl ethers according to the invention are useful as herbicides both before and after the plants have become visible suitable. Herbicides, which take effect before the plants become visible, are used to treat the soil, in which the species is to be planted, before, during, or in most cases after Treat the seeds and before the plants become visible. Herbicides that are effective after the plants become visible are used after the plants have become visible and during the plants' growing season.

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The cultivated plants for the protection of which the diphenyl ethers according to the invention can be used with advantage include e.g. cotton soybeans, peanuts, saffron, beans, Peas, carrots, corn, wheat and other grains.

Diphenyl ethers according to the invention are also suitable for controlling weeds in rice crops. If they are in When using replanted rice crops, the ethers can be applied either before or after the weeds become visible that is, they are the growth medium of the transplanted plants, either before the weeds become visible or, while the weeds are in the early stages of their growth, can be added. The ethers can can be added to the growth medium both before and after the rice is transplanted into the medium.

The diphenyl ethers according to the invention can be used in any amounts that can prevent the growth of weeds- » can be applied. A preferred amount for the application of the herbicides is from about 11 to about 1345, particularly preferred at about 28 to about 447 grams of diphenyl ether per 1000 m (0.1 to 12, preferably 0.25 to 4 lbs per acre).

In some cases the diphenyl ethers can be used according to the invention be incorporated with advantage in the soil or some other growth medium prior to planting or sowing the plants. These Incorporation can take place by any known means, e.g. by simply mixing with the ground, by applying of the diphenyl ether on the surface of the soil and subsequent plowing or Einggen on the desired Ground depth or by applying a liquid vehicle to the required. To achieve impregnation and penetration depth.

The diphenyl ethers according to the invention can be used as herbicides for the growth medium or the plants to be treated either all of them or, preferably, as a component of one

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herbicidal composition or formulation containing an agriculturally acceptable carrier may be added. By agriculturally acceptable carrier is meant any substance which can be used to dissolve, disperse or distribute the herbicidal compound without reducing the effectiveness of the herbicidal compound, the carrier not adversely affecting soil, equipment, which has crops and the agricultural environment. Mixtures of the diphenyl ethers according to the invention can also be used in such herbicidal formulations. These herbicidal compositions according to the invention can be either solid or liquid formulations or solutions. ¹ as the diphenylether for example as wettable powders, emulsifiable concentrates, powdery preparations, granular formulations, aerosols, or flowable emulsion concentrates can be formulated. In such formulations, the herbicidal compounds are diluted with a liquid or solid carrier and optionally suitable surfactants are also added.

The invention also includes a process for producing the herbicidal composition in which a new herbicidal Diphenyl ether is brought into a suitable form for application, i.e. with a solid and / or liquid carrier and optionally blended with a surfactant, an adhesive and other common additives.

As a rule, especially in applications after the plants have become visible, it is advantageous to add additives such as wetting agents, distributing agents, dispersing agents, adhesives, adhesives and the like. For a more complete description of such additives see the publication by John W, McCutcheon, Inc. "Detergents and Emulsifiers Annual".

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The diphenyl ether compounds according to the invention can in be dissolved in a suitable solvent. Examples of suitable solvents are alcohols, ketones, aromatic Hydrocarbons, halogenated hydrocarbons, Dimethylformamide, dioxane, dimethyl sulfoxide and the like mixtures of these solvents can also be used. The concentration of. Solution can be between about 2 to about 98%, with a preferred range of about 25% up to about 75%.

For the preparation of emulsifiable concentrates you can use the diphenyl ether in an organic solvent, such as Benzene, toluene, xylene, methylated naphthalene, corn oil, pine oil, o-dichlorobenzene, isophorone, cyclohexanone, methyl oleate and the like, or mixtures of these solvents, adding an emulsifying agent capable of dispersing permitted in water. Suitable emulsifying agents include E.g. an: ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids and of reactive Amines and partially esterified polyhydric alcohols. Solvent-soluble sulfates or sulfonates, such as the alkaline earth salts or amine salts of alkyl benzene sulfonates and the fatty alcohol sodium sulfates with surface-active properties can be used alone or in admixture with an ethylene oxide reaction product can be used as emulsifiers. Flowable emulsion concentrates are more similar Formulated like emulsifiable concentrates and include, in addition to the aforementioned components, water and a stabilizer, such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentration of the active ingredients in the emulsifiable concentrates is usually about 10 to 60% and in In the case of the flowable emulsion concentrates, it can rise as high as up to about 75%.

Wettable powders that can be sprayed can be prepared by mixing the active compound with a finely divided solid

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substance, such as a clay, inorganic silicates and carbonates, Manufacture of silicas, and addition of wetting agents, adhesives and / or dispersants. The concentration the active ingredient in such formulations typically ranges from about 20 to 98%, preferably about 40 to about 75%. The dispersant can be about 0.5 to about 3% and the wetting agent about 0.1 to about 5% the preparation.

Dust-like preparations can be produced by mixing the compounds according to the invention with finely divided, inert solids, which can be organic or inorganic in nature. Suitable materials of this type are botanical flours, silicas, silicates, carbonates and clays. A convenient method of preparing a powdered formulation is to dilute a wettable powder with a finely divided carrier. In the rule, ^v dust-like concentrates are prepared, which contain about 20 to 80% of active ingredient and are usually diluted subsequently to a concentration of 1 to 10% of their use.

Granular formulations can be obtained by adding granular solids such as fuller's earth, vermiculite, crushed corn on the cob, Seed husks, including bran and husks of other grains or similar materials with the active ones Impregnated fabrics according to the invention. One can use a solution of one or more diphenyl ethers in a volatile Spray or mix organic solvent onto the granular solid and then use the solvent remove by evaporation. The granular material can have any particle size, with particles having a Size between 16 and 60 meshes are preferred. The granular formulation usually contains about 2 to 15% of the diphenyl ether.

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The diphenyl ethers according to the invention can also be mixed with artificial fertilizers or other fertilizers before their application will. In the case of a fixed combination that contains the artificial fertilizer and the diphenyl ether, particles of the artificial fertilizer become or another fertilizer, such as ammonium sulfate, Ammonium nitrate or ammonium phosphate coated with one or more ethers. But you can also use the solid diphenyl ethers and the solid artificial fertilizers using each other Mix the usual equipment, or you can also make granular preparations from artificial fertilizers and the Diphenyläthera. All possible amounts of diphenyl ether and artificial fertilizers can be used for as long as possible these are favorable for the crops and the weeds to be destroyed are harmful. In such fertilizer preparations but the diphenyl ether concentration is usually about 5 to about 25%. Promote these preparations the rapid growth of the desired plants and at the same time control the growth of the undesired plants.

The diphenyl ethers according to the invention can be used as herbicides Sprays can be applied by the known methods, e.g. by conventional hydraulic sprays or dusty Preparations. For applications with a low volume requirement, a solution of the connection is usually used. The degree of dilution and the amount used will usually depend on such factors as the type of the equipment available, the application method, the area to be treated and the type and growth phase of the weed species ·

For some applications it can be advantageous to combine one or more other herbicides with the diphenyl ethers to apply according to the invention. Examples of such other herbicides that can be used to advantage with the herbicides after of the invention are the following compounds:

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2

Carboxylic acids and their derivatives ι

2,3,6-Trichlorobenzoic acid and its salts 2,3,5,6-Tetrachlorobenzoic acid and its salts 2-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-methoxy-3,6-dichlorobenzoic acid and its salts 2-methyl-3,6-dichlorobenzoic acid and its salts 2,3-dichloro-6-methylbenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 2,4,5-trichlorophenoxyacetic acid and its salts and esters 2-methyl-4-chlorophenoxyacetic acid and its salts and esters 2- (2,4,5-Trichlorophenoxy) propionic acid and its salts and esters 4- (2,4-Dichlorophenoxybutyric acid and its salts and esters 4- (2-methyl-4-chlorophenoxy) butyric acid and its salts and

Ester ^ -

2,3,6-trichlorophenylacetic acid and its salts 3 1 6-endoxohexahydrophthalic acid dimethyl 2,3,5,6-tetrachloroterephthalate trichloroacetic acid and its salts. 2,2-dichloropropionic acid and its salts 2,3-dichloroisobutyric acid and its salts

Carbamic acid derivatives

Ethyl-N, N-di (n-propyl) thi oils arbamate Propyl N, N-di (n-propyl) thiol carbamate, ethyl N-ethyl-N- (n-butyl) thiocarbamate Propyl N-ethyl-N- (n-butyl) thiolearbamate 2-chloroallyl-N, N-diethyldithiocarbamate N-methyldithiocarbamic acid salts Ethyl 1-hexamethyleneimine carbothiolate Isopropyl N-Phenyl Carbamate Isopropyl N- (m-chlorophenyl) carbamate 4-chloro-2-butynyl-N- (m-chlorophenyl) carbamate Methyl N- (3ι4-dichlorophenyl) carbamate

Phenols

Dinitro-o- (sec-butyl) phenol and its salts Pentachlorophenol and its salts

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Substituted ureas

3- (3,4-dichlorophenyl) -1,1-dimethylurea 3-phenyl-1,1-dimethylurea

3- (3,4-dichlorophenyl) -3-methoxy-1,1-dimethylurea

3- (4-chlorophenyl) -3-methoxy-l, 1-dimethylurea 3- (3 1 4-dichlorophenyl) -1-n-butyl-l-methylurea 3- (3,4-dichlorophenyl) -1-methoxy- l-methylurea 3- (4-chlorophenyl) -1-methoxy-l-methylurea 3- (3,4-dichlorophenyl) -1,1,3-trimethylurea 3- (3,4-dichlorophenyl) -1,1-diethylurea f dichloralurea

Substituted triazines 2-chloro-4,6-bis (ethylamino) -s-triazine Z-chloro ^ -äthylamino-e-isopropylamino-s-triazine 2-chloro-4,6-bis (methoxypropylamino) -s-triazine 2- Methoxy-4,6-bis (isopropylamino) -s-triazine 2-chloro-4-ethylamino-6- (3-methoxypropylamino) -s-triazine 2-methylmercapto-4,6-bis (isopropylamino) -s-triazine 2 -Methylmercapto-4,6-bis (ethylamino) -s-triazine 2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-methoxy- 4,6-bis (ethylamino) -s-triazine 2-Me1 ^ oxy-4-ethylamino-6-isopropylamino-s-triazine 2-methylmercapto-4- (2-methoxyethylamino) -6-isopropylamino-triazine

Diphenyl ether derivatives

2,4-dichloro-4-nitrodiphenyl ether 2,4,6-trichloro-4-nitrodiphenyl ether 2,4-dichloro-6-fluoro-4-nitrodiphenyl ether 3-methyl-4-nitrodiphenyl ether, 3,5-dimethyl-4-nitrodiphenyl ether 2,4-Dinitro-4-trifluoromethyldiphenyl ether 2,4-dichloro-3 * -methoxy-4'-nitrodiphenyl ether

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Anilide

N- (3,4-dichlorophenyl) propionamide N- (3,4-dichlorophenyl) methacrylamide N- (3-chloro-4-methylphenyl) -2-methylpentanamide N- (3,4-dichlorophenyl) trimethylacetamide N- (3,4-dichlorophenyl) -alpha, alpha-dimethylvaleramide N-isopropyl-N-phenylchloroacetamide N-n-butoxymethyl-N- (2,6-diethylphenyl) chloroacetamide N-n-methoxymethyl-N- (2,6-diethylphenyl) chloroacetamide

Uracile ■

5-Bromo-3-s-butyl-6-methyluracil 5-Bromo-3-cyclohexyl-1,6-dimethyluracil 3-cyclohexyl-5,6-trimethyleneuracil 5-bromo-3-isopropyl-6-methyluracil 3-tert-butyl-5-chloro-6-methyluracil

Nitriles

2,6-dichlorobenzonitrile

Diphenylacetonitrile

3 1 5-dibromo-4-hydroxybenzonitrile 3 f 5-diiodo-4-hydroxybenzonitrile

Other organic herbicides

2-chloro-N _f N-diallylacetamide

N- (1,1-Dimethyl-2-propynyl) -3,5-dichlorobenzamide Maleic hydrazide

3-amino-1,2,4-triazole

Monosodium methanar sonate

Disodium methanars onate

N, N-dimethyl-alpha, alpha _r diphenylacetamide N, N-di (n-propyl) -2,6-dinitro-4-trifluoromethylaniline N, N-di (n-propyl) -2,6-dinitro-4- methylaniline N, N-di (n- ^ ropyl) -2,6-dinitro-4-methylsulfonylaniline

0- (2,4-dichlorophenyl) -O-methyl-isopropylphosphoramido thioate

4-amino-3 »5,6-trichloropicolinic acid 2,3-dichloro-1,4-naphthoquinone

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Di (methoxythiocarbonyl) disulfide

3-Isopropyl-1H-2,1,3-benzothiadiazine- (4) 3H-one-2,2-dioxide

6,7-Dihydrodipyridol (1,2-a: 2 ·, 1'-c) pyrazidiniumsalze 1,1'-dimethyl-4,4 ^f -bipyridiniumsalze

3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine.

If mixtures of the herbicides are used, the relative proportions of the individual components depend on the type of herbicide treated crop and the desired degree of selectivity in weed control.

The biphenyl ethers according to the invention or their precursors can be obtained by any known method for the preparation of analogous compounds by using an appropriate one substituted phenol or the potassium or sodium salt of phenol with an appropriately substituted halobenzene such as Chlorobenzene or fluorobenzene, in the presence of an alkaline agent.

The invention is explained in more detail in the following examples. In Table I typical diphenyl ethers according to the invention with Z = H are given their melting points and their Elemental analysis listed. The specific preparation of typical compounds is given below for the examples 1 to 3 and 6 to 8 according to Table I explained.

In Table II, further typical diphenyl ethers are listed with details of their melting points and elemental analyzes. The preparation of specific compounds in which the symbol Z is a group or atom other than hydrogen represents is illustrated in the following examples, where the letter Z after it means that it is to make a compound where Z is a group or atom other than hydrogen.

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Table I. Diphenvlether - Physical data

CF

NO,

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example
No. .. χ Y Mp (bp) ° C found
ber. % C analysis 9.29
9.09 96 "Cl % F , ■ ■ ro
co • 1 • CN H 93-98 found
ber. 54.83
54.56 λ / ττ
/ vfl 4.44
4.41 15.84
18.49 r— '
VO
I. (J)
CJ
OO 2 Cl H 67-70
C ₁₃ H ₇ ClF ₃ NO ₃ found
ber. 49.31
49.19 2.33
2.29 4.77
4.59 11.15
11.21 17.80
17.94 3 F. H (95-98 / 0.35 mm)
C ₁₃ H ₇ F ₄ NO ₃ found
ber. 51.77
51.16 2.15
2.22 3.63
3.87 15.73 26.21 co 4th Br H 86-87
C ₁₃ H ₇ BrF ₃ NO ₃ found
ber. 43.44
43.10 2.50
2.31 4.73
4.95 22.13 *
22.07 * 15.85
15.74 098 5 H H 47-48
C ₁₃ H ₈ F ₃ NO ₃ found
ber. 55.42
55.12 1.78
1.95 4.04
3.98 19.85
20.13 39/1 6th Cl ⁷ Cl 83-86
C ₁₃ H ₆ Cl ₂ F ₃ NO ₃ found
ber. 44.24
44.33 3.00
2.85 5.29
4.71 20.15
20.13 15.98
16.19 235 7 / / CH ₃ H 58-63.5
C ₁₄ H ₁₀ F ₃ NO ₃ found
ber. 56.15
56.57 1.42
1.72 3.81
3.99 18.93
19.18 8th CF ₃ H 72-73
C ₁₄ H ₇ F ₆ NO ₃ 48.33
47.87 3.50
3.39 30.48.
32.46 * 96Br 2.09
2.01

example 1

Production of 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-

4-nitrophenyl ether

A solution of potassium hydroxide (-3.2 g; 0.05 mol of one Purity of 89.3%) and p-nitrophenol (7.0 g; 0.05 mol) in methanol (25 ml) is removed from the solvent under reduced pressure freed. The residue is dissolved in tetramethylene sulfone (sulfolane), then 4-chloro-3-cyan-alpha, alpha, alpha-trifluorotoluene (10.3 g; 0.05 mol) was added and the obtained solution is heated to 150 ° C. for five hours. After cooling, the solution is diluted with benzene (350 ml), washed with water (6 × 250 ml), dried, and the solvent will be removed. The residue (12.5 g) is recrystallized from isopropanol, 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether (7.6 g; 49%) with a melting point of 93-98 ° C.

Example 2

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-

4-nitrophenyl ether

Ia) 2-chloro-alpha _t alpha, alpha-trifluoro-p-cresol Chlorine gas is poured into a solution of alpha, alpha, alpha-trifluoro-p-cresol (4.5 g; 0.025 mol) in ethylene dichloride ( 200 ml) at 0 ° C until the theoretical volume has been absorbed. The solvent is driven off and the residue is distilled, 2-chloro-alpha, alpha, alpha-trifluoro-p-cresol (3.5 g; 74%) with a boiling point of 80-82 ° C. at 33 mm being obtained .

Ib) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

phenyl ether

It becomes potassium hydroxide (1.08 g; 0.0166 mol; of 86% purity) dissolved in methanol (10 ml) and a solution of 2-chloro-r alpha, alpha, alpha-trifluor-p-cresol (3.27 g; 0.0166 mol) in methanol was added. The solvent will

309839/1235

removed under pressure and tetramethylene sulfone (100 ml) and then added p-fluoronitrobenzene (2.34 g; 0.0166, mol) and then the mixture is heated to 130-150 ° C for seven hours. After cooling, the solution is in water poured (200 ml) and extracted with benzene. The extract is dried, filtered through activated silica gel (10 g) and the solvent is removed. The residue is taken up in isopropanol / hexane cooled to -20 ° C. and decanted from the oily precipitate and the solvents are driven off. The residue (2.9 g) is distilled, using 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether (1.6 g; 31%) with a boiling point of 23 - 85 ° C at 0.3 mm, which forms crystals with a melting point of 62-68 ° C. when inoculated. As an impurity is in this manufacturing process 4-carbo-methoxy-2-chlorophenyl-4-nitrophenyl ether isolated and identified.

Ha) 2-chloro-alpha.alpha «alpha-trifluoro-p-tolvl-phenyl ether Potassium phenoxide, which is obtained by distilling a solution of phenol (4.7 g; 0.05 mol) and potassium hydroxide (3.3 g; 0.05 Mol; 86.2% purity) in methanol (20 ml) is dissolved in tetramethylene sulfone (75 g) and 3,4-dichloroalpha, alpha, alpha-trifluorotoluene (10.8 g; 0.05 mol) is added . The mixture is heated to 170 ° C. overnight and then cooled, diluted with benzene (250 ml) and washed with water (3 × 600 ml). The organic phase is dried, filtered through activated silica gel (20 g) and the solvent is removed. The residue (12.4 g) is distilled to give 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-phenyl ether (9.9 g; 72%) having a boiling point 85-90 ° C / 0.25 mm receives. About 5% 6-chloro-alpha, alpha, alpha-trifluoro-m-tolylphenyl ether is present as an impurity.

Elemental analysis

Found: C, 57.13; H 3.09; Cl 13.17; F 20.86 calcd for: C ₁₃ H ₈ ClF ₃ O; C 57.27; H 2.95; Cl 13.00; F 20.91

309839/1238

b) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

phenyl ether ;

A mixture of fuming nitric acid (IO g; 0.16 mol) and concentrated sulfuric acid (10 g) are converted into 2-chloro-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether with vigorous stirring (27.3 g; 0.01 mol) are added at 75 ° C, and then such a rate of addition is maintained that the Temperature does not rise above 85 ° C. After stirring at 80 ° C for half an hour, it becomes more mixed acid (5 g + 5 g) is added and the mixture is stirred for 15 minutes, cooled, diluted with water and then with benzene (2 × 200 ml) extracted. The extract is washed with water and with bicarbonate solution, dried, and the solvent will be removed. The residue (29.1 g) is recrystallized from isopropanol, with 2-chloro-alpha, alpha, alphatrifluoro-p-tolyl-4-nitrophenyl ether (12.7 g; 40%) with a melting point of 67-70 ° C can be obtained. The analytical and spectroscopic data confirm the identity of the products made on routes I and II.

Example 3

Production of 2, alpha, alpha, alpha-? Etrafluor-p-tolyl-4-

nitrophenyl ether

a) 2-amino-alpha, alpha _t alpha-trlfluoro-p-tolylphenyl ether

2-nitro-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (57.0 g; 0.209 mol) are dissolved in ethanol (200 ml) and placed in a hydrogen atmosphere in a Parr apparatus in the presence of Platinum oxide (100 mg) shaken until the absorption is stopped. The catalyst is removed by filtration, and that

Solvent is driven off, with 2-amino-alpha,

a ^ pha, alpha-trifluoro-p-tolylphenyl ether (50.3 g; 99%) is obtained,

which is used without further purification.

Elemental analysis

found: C, 61.76; H 3.65; F 22.35; N 5.52

calculated for: C ₁₃ H ₁₀ F ₃ NO; C 61.66; H 3.98; F 22.51; N 5.53.

309839/1235

b) 2, alpha _t alpha, alpha-tetrafluoro-p-tolylphenyl ether, 2-amino-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (25.3 g; 0.1 mol) are added to concentrated hydrochloric acid (100 ml) and the mixture is cooled to -15 ° C. A solution of sodium nitrite (7.5 g; 0.1 + mol) in water (5 ml) is added dropwise with stirring. After a total of 2 hours at -15 ° C., the diazonium chloride solution is filtered off and treated with a solution of sodium fluoroborate (25 g; 0.2 + mol) in water (30 ml). The dense fluoroborate salt is filtered off and washed with ethanol and ether and then air dried. The product, which has a decomposition point of about 190 ° C., is obtained in a yield of 23.0 g. The salt is then added dropwise to a flask kept in a 200 ° C oil bath. When the decomposition has ended, the residue is taken up in benzene (150 ml), washed with water (4 × 100 ml), dried, and the solvent is removed. The residue (10.3 g) is extracted with isopropanol / hexane, leaving a residue which, in the distillation, 2, alpha, alpha, alpha-tetrafluoro-p-tolylphenyl ether (3.4 g; 14%) with a boiling point of 90 ° C / 0.25 mm results.

c) 2.alpha.alpha.alpha-tetrafluoro-p-tolyl-4-nitrophenyl ether The material prepared above is nitrated using the above procedure of Example 2, with 2-chloro-alpha, alpha, alpha-tetrafluoro-p-tolyl-4 -nitrophenyl ether is formed.

Example 6

Production of 2,6-dichloro-alpha, alpha, alpha-trifluor-p-

tolyl-4-nitrophenyl ether

a) 3,4-dichloro-alpha, alpha, alpha-trifluoro-5-nitro-toluene

and 3,4-dichloro-alpha , alpha.alpha-trifluoro-6-nitrotoluene A mixture of 3,4-dichloro-alpha, alpha, alpha-trifluorotoluene (430 g; 2.0 mol), concentrated sulfuric acid (1200 ml) and concentrated Nitric acid (1200 ml, excess) is used in

309839/1235

90-100 ° C for half an hour. The mix will then cooled and the acidic phase is discarded. The organic phase is washed, first with water, then with dilute sodium bicarbonate solution, potassium carbonate solution, then dried and distilled, an approximately equal mixture (456 g; 89%) of 3,4-dichloro-alpha, alpha, alpha-trifluoro-5-nitrotoluene and 3,4-dichloro-alpha, alpha, alpha-trifluoro-6-nitrotoluene with a boiling point of 86 ° C / 3mm is obtained.

b) 2-chloro-alpha, alpha, alpha-trifluoro-6-nitro-p-tolyl phenyl ether

A solution of potassium hydroxide (43.2 g; 86% purity; 0.665 mol) in water (20 ml) is slowly added to a mixture of phenol (62.5 g; 0.665 mol) and the product of (a) (450 g in total; equivalent of 0.665 mol of 3,4-dichloro-alpha, alpha, alpha-trifluoro-5-nitrotoluene) in tetramethylene sulfone (300 ml) at 30-68 ° C. with stirring . After stirring at 42-68 ° C. for a total of one hour, the mixture is diluted with hexane (400 ml) and water (600 ml). The resulting liquid layers are separated and the aqueous phase is extracted once with hexane. The combined organic phases are washed with water and then with dilute sodium hydroxide solution, dried, and the solvent is removed. The residue (471.3 g) is distilled through a Vigreux column with a vacuum jacket. The fractions had the following composition: No. 1 (272.2 g) b.p. 100 ° C / 0.2 mm consisted essentially of unreacted 3,4-dichloroalpha, alpha, alpha-trifluoro-6-nitrotoluene No. 2 ( 196.2 g) b.p. 109-119 ° C. / 0.2 mm consisted essentially of the desired diphenyl ether. A small residue (3.5 g) was discarded. No. 2 crystallized and was recrystallized from 2-propanol (600 ml) at 0 ° C., 2-chloro-alpha, alpha, alpha-trifluoro-6-nitro-p-tolylphenyl ether (144 g; 68-6) melting point 57-61 ° C was obtained.

309839/1235

c) 2-Amino-6-chloro-alpha, alpha, alpha-trifluoro-p-tolyl phenyl ether

A solution of 2-chloro-alpha, alpha, alpha-trifluoro-6-nitrop-tolylphenyl ether (150 g; 0.472 mol) in ethanol (1200 ml) is dissolved in a hydrogen atmosphere in a Parr apparatus in the presence of PtO ₂ (600 mg ) shaken until the exposure is finished. The catalyst is filtered off, the solvent removed, the residue taken up in pentane (600 ml), the solution filtered through activated silica gel (about 15 g) and the solvent removed. The residue is recrystallized from pentane at -20 ° C, 2-amino-6-chloro-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (94.1 g; 70Ji) with a melting point of 47-53 ° C receives.

d) 2.6-dichloro-alpha.alpha.alpha-trifluoro-p-tolvlphenvläther 2-Amino-6-chloro-alpha, alpha, alpha-trifluoro-p-tolylphenylether (5.8 g; 0.02 mol) is concentrated in Hydrochloric acid (70 ml) crushed, whereby a suspension of the amine hydrochloride is formed. A solution of sodium nitrite (1.5 g; 0.022 mol) in water (3 in) is added dropwise to the stirred suspension at -15 ° Q. The mixture is then stirred for 50 minutes at +3 - -10 ° C and then filtered through a sintered glass filter. The filtrate is slowly added to a suspension of copper-I chloride (3.0 g) in concentrated hydrochloric acid (20 ml) at -3 - -10 ° C, then the temperature is slowly increased, finally to 90 ° C for 20 Minutes. The mixture is then cooled and neutralized with solid sodium bicarbonate and extracted with ether. The extract is washed with water and sodium carbonate solution, dried and freed from the solvent. The residue is distilled to give the diphenyl ether (3.5 g) as a crystallizing oil. The solid is taken up in pentane (10 ml) and filtered through activated silica gel (approx. 5 g) and the solvent is removed. The residue (3.3 g) is recrystallized from 2-propanol, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (2.75 g; 45 #) with a melting point of 48 ° -50 ° C. being obtained will.

309839/1235

. β) 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

phenyl ether

2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (1.7 g; 0.0055 mol) becomes a cold (0 ° C) mixture of concentrated sulfuric acid (1.7 g) and concentrated Given nitric acid (1.2 g). The mixture is heated to 30.degree.-35.degree. C. and at this temperature for 30 minutes touched. It is then diluted with water and extracted with benzene / pentane. The extract is made with sodium bicarbonate solution and water, then dried and freed from the solvent. The residue will result in a Similar experiment combined with 500 mg of the starting material and recrystallized from 2-propanol, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitrophenyl ether Cl »9 g; 75%) with a melting point of 83 - 66 ° C.

Example 7

Production of alpha, alpha, alpha -Trifluor ^^ - xylyl ^ - nitrophenvläther

a) 2-Bromo-alpha.alpha.alpha-trifluoro-p-tolvlphenyl ether A solution of 3-bromo-4-chloro-alpha, alpha, alpha-trifluorotoluene (143 g; 0.55 mol), potassium phenoxide (72.6 g; 0.55 mol) in tetramethylene sulfonone (200 ml) is heated to 165-170 ° C. for 3 hours while stirring. The solution is then cooled. Benzene (250 ml) and hexane (250 ml) are added and the solution is washed with dilute sulfuric acid (500 ml), the solvent is removed and the oil is distilled, using 2-bromo-alpha, alpha, alpha- trifluorop-tolylphenylether (124 g; 7196) with a boiling point of

100 - 105 ° C / 0.45 mm.

"444

b) alüha. alpha .alpha -trifluoro-2,4-xvlylphenyl ether n-butyllithium, 15 # / hexane solution (50 ml; 0.083 mol) becomes. to a stirred solution of 2-bromo-alpha, alpha, alpha-trifluorop-tolylphenyl ether (25.36 g; 0.08 mol) and hexane (300 ml) under nitrogen and stirred at 25 ° C. for 10 minutes.

309839/1235

Dimethyl sulfate (25 g; 0.2 mol) is added in one shot and the mixture is allowed to reflux gently for 10 minutes warmed, poured onto ice, and the aqueous phase is discarded. The hexane solution is washed with water, dried, the solvent is removed, and the distilled oil is alpha, alpha, alpha -trifluoro-2,4-xyIylphenyläther with the boiling point of 86 - 88 ° C / 0.3 mm.

c) Alpha .alpha \ alpha -TrIfluoro-2,4-xylyl-4-nitrophenvlether A cooled mixture of concentrated sulfuric acid (14 ml; 0.25 mol) and concentrated nitric acid (14 ml; 0.22 mol) is stirred to a solution of 2-methyl-alpha, alpha, alpha-trifluoro-p-tolylphenyl ether (17.8 g; 0.07 mol) and 1,2-dichloroethane (60 ml) at 6-14 ° C in 74 minutes and for 70 Stirred for minutes at 10-15 ° C. The oil layer is separated and washed with water, then with 10% carbonate solution and twice with water. The solvent is removed and the product which has crystallized out from hexari / isopropanol is alpha, alpha, alpha-trifluoro-2,4-xylyl-4-nitrophenyl ether (6.3 g; 30%) with a melting point of 58 63.5 ° C

Example 8

Production of alpha, alpha, alpha, alpha ', alpha', alpha'-hexa-

fluoro-2.4-xvlyl-4-nltrophenvlether

a) alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro-2,4-

xvlvlphenvläther

A solution of potassium phenoxide (15.0 g; 0.1 mole) and 4-chloralpha, alpha, alpha, alpha *, alpha ', alpha * -hexafluoro-m-xylene in Tetramethylene sulfone (50 ml) is heated to 140-160 ° C. for 60 hours warmed up. The solution is cooled and benzene (400 ml) and hexane (250 ml) are added and the solution is washed twice with Water (1 liter, 500 ml), twice with 10% sodium carbonate solution (about 200 ml each) and water, dried, filtered through activated silica gel (about 25 g), the solution

309839/1235

231163a

agents are removed and the residue is distilled, where one is alpha, alpha, alpha, alpha ', alpha', alpha '-hexaf luoro-2,4-xylylphenyl ether (22.4 g; 73%) with the boiling point of 81 -. 85 ° C / 1 mm is maintained.

b) alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro, 2,4-

xylyl-4-nitrophenyl ether

alpha, alpha, alpha, alpha ', alpha', alpha'-hexafluoro-2,4-xylylphenyl ether (16.1 g; 0.0525 mol), concentrated sulfuric acid (12 ml ι 0.22 mol), concentrated nitric acid (12 ml; 0.19 mol) and ethylene dichloride (65 ml) are stirred for 30 minutes at room temperature and then left to stand to separate. The ethylene dichloride layer is washed with water, then with a 10% sodium carbonate solution and then again with water. Then the solvent is removed. The remaining oil is dissolved in hexane, filtered through activated silica gel (about 25 g), and the solvent is removed, alpha, alpha, alpha, alpha ', alpha, alpha ^f -Hexaf luor-2,4- xylyl-4-nitrophenyl ether (11.4 g; 62%) with a melting point of 72-73 ° C. is obtained.

Examples 9-14

Following the procedure of Examples 1-3, other diphenyl ethers are obtained of formula I produced. To the connections,

that are produced by these processes include:

6-chloro-alpha, alpha, alpha, alpha ¹ , alpha ¹ , alpha'-hexafluoro-2,4-

xylyl-4-nitrophenyl ether,

2-chloro-6, alpha, alpha, alpha-tetrafluoro-p-tolyl-4-nitro-

phenyl ether,

alpha, alpha, alpha-triflupr-2-iodo-p-tolyl-4-nitrophenyl ether, 2-cyano-6-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-4-nitro-

phenyl ether,

2-bromo-alpha, alpha, alpha -4,6-xylyl-4-nitrophenyl ether and 2-chloro-alpha, alpha, alpha, alpha ', alpha ·, alpha' -4,6-xylyl-4-

nitrophenyl ether.

These diphenyl ethers have herbicidal effects.

3098 39/1235

The diphenyl ethers according to the invention can also be correctly designated using other nomenclature systems. For example, the diphenyl ether of Example 1 can also be used 2-cyano-4-trifluoromethyl-4'-nitrodiphenyl ether may be mentioned. The nomenclature usually used here corresponds to those of the journal "Chemical Abstracts".

309839/1236

■ Table II

Diphenyl ether - Physical data

CF,

236 example X Y Z NO ₂ found
calc. No. mFp. ( ⁰ C) found
calc. 1 line H H OC ₂ H ₅ found
calc. 2 Z Cl H OCH ₃ 72-75 found
calc. 3 Z Cl H OC ₂ H ₅ 95-100 4 Z Cl H 0C ₃ H _? -i 83-84 49.5-51

analysis

% C ^ H

54.67 3.75 4.19
55.05 3.70 4.28

15.25 17.42

found 48.78 2.89 4.01 9.65 14.91 calc. 48.33 2.61 4.03 10.20 16.40

49.85 3.33 3.68

49.80 3.07 3.87

51.02 3.58 3.52

51.18 3.49 3.73

9.62 15.58 9.42 15.16

9.90 15.51 ^ 9.80 15.75 - *

CD U) CO

example 5 Z No. 6th Z 7th Z co O 8th Z co OO co 9 Z (D 10 Z co cn

Table II (continued)

XYZ mFp. ( ⁰ C)

Cl H ΟΟχΗ ,, - η 75-76 found. 51.36 3.60 3.62 9.34 15.00

⁵ 'calc. 51.18 3.49 3.73 9th, 42 15.16

Cl H OCaH ₀ -II 51-52 found. 52.07 4.03 3.38 9.28 14.65

* ^y calc. 52.42 3.88 3.59 9.10 14.63

CN H OC ₅ Hc 143-145 found. 54.84 3.36 8.01 15.85

* ^p calc. 52.18 3.01 7.61 15.48

CN H 0C, H ₇ -n 96.5-98 found. 55.70 3.65 7.56

^ 'calc. 55.74 3.58 7.65 15.56

CN H CH, 86-88.5 found. 55.95 2.80 8.62 17.68

· * Calc. 55.90 2.81 8.72 17.69

Cl H OH 68-70 found. 47.07 2.11 4.00 10.76 17.00

calc. 46.79 2.12 4.20 10.63 17.08

Z Cl H OCH ₉ CF _x 78-80 found 43.30 1.77 3.22 8.60 2 ^ .60

^{2 3} calc. 43.35 1.94 3.37 8.54 27.40

Z Cl H OCH ₅ CH = CH ₉ 76-78.5 found. 51.76 2.77 3.75

. ² * calc. 51.42 2.97 3.75

Z Cl H OCH ₅ = ¹ CH 89-93 found. 51.83 2.22 3.52

² calculated 51.70 2.44 3.77

Z Cl H OCH ₅ CH ₅ C = CCH, 93-94 found. 53.99 2.95 3.35

²² ^ calc. 54.10 3.28 3.50

9.51 * 15.32 KJ 9.48 15.25 Q) 9.61 15.31 9.54 15.33 σ> Q) 8.93 14.12 OD 8.87 14.25

example
No. X
Cl Y
H Z
DCH ₂ CH ₂ OH Table II (Continuation) found
calc. 47.53
47.70 2.9 "2
2.94 3.55
3.71 flCl
9.88
9.38 14.98
15.09 - 1 ■ CJ 15 Z Cl H OCH ₂ CH ₂ OC ₂ H ₅ mFp. ( ⁰ C) found
calc. 50.75
50.32 3.82
3.73 3.37
3.45 8.48
8.74 14.00
14.05 iv:
1 cn
CO
OO 16 Z Cl
Cl
Cl H
H
H OCH ₅ CH ₉ N (CH,)
H
OCOCH ₃
NHC ₂ H ₅
I. 76-77 found
calc.
found
calc.
found
calc. 50.30
50.44
47.82
47.90
50.01
49.94 3.76
3.98
2.50
2.42
3.23
3.35 6.42
6.92
3.65
3.73
7.82
7.77 9.19 '
8.76
9.58
9.44
9.95
■ 9.83 13.80
14.03
14.79
15.20
15.48
15.80 17 Z
18 Z
19 Z Cl H N (CH ₃ J ₂
Ii 62-64 found
calc. 50.27
49.97 3.46
3.35 7.95
7.77 9.62
9.83 15.50
15.80 20 Z Cl H N (C ₂ H ₅ ) _{2 2} oil
85-89
82-83 found
calc. 52.80
52.50 3.89
4.15 7.10
7.20 9.25
9.12 14.58
14.68 309839/1 21 Z Cl H NHCH ₂ CH ₂ OH 82-83 found
calc. 46.22
47.82 3.33
3.21 7.06
7.44 8.50
9.42 15.30
15.13 235 22 Z Cl H OCH ₂ CO ₂ H. * 170 ° C /
0.01 mm found
calc. 45.96
46.00 2.21
2.32 3.71
3.57 9.17
9.05 13.99
14.56 23 Z Cl H OCH ₂ CO ₂ C ₂ H ₅ 85-87 found
calc. 48.49
48.60 2.93
3.13 3.25
3.34 8.58
8.46 13.65
13.62 24 Z * Boiling point 94-96 76-77

example
No. ■ - - Ii 25 Z X I. Table II (continued) Ά ^ Fp. ( ⁰ C) «• f.
calc. 47.34
47.35 2.63
2.73 * ^m KCl 26F • I. ·· (I. 26 Z Cl H OCH (CH ₃ ) COgH 108-109 ' found
calculate 49.78
49.85 3.40
3.49 3.52
3.45 8.78
8.73 13.70
14.05 VX
V »
I. 27 Z Cl H OCH (CH ₃ ) CO ₂ C ₂ H ₅ 71-72.5 found
calc. 48.6
46.93 2.87
2.42 3.07
3.23 8.31
8.18 12.90
13.15 28 Z / Cl H NH ₂ 85.5-89.5 gef ·
calc. 50.61
50.70 3.39
3.50 8.01
8.42 10.37
10.66 17.09
17.14 29 Z Cl H HO ♦ 180-185 /
0.04 mn found
calc. 52.67
53.00 3.05
2.87 6.80
6.96 8.95
8.80 13.71
14.15 088: * 30 Z Cl H OCHgCHgSCH 104-105.5 found
calc. 52.59
53.00 2.77
2.87 3.44
3.63 9.41
9.20 14.33
14.80 to 31 Z Cl H OCH (CH ₃ ) CSCH 40-42 found
calc. 50.44
50.60 3.27
3.25 3.61
3.63 9.66
9.20 15.27
14.80 1235 32 Z Cl H OCHgCHgCOCH ₃ 74-76 found
calc. 48.07
50.60 3.26
3.25 3.36
3.47 8.81
8.75 14.49
14.12 33 Z. Cl H OCH (CH ₃ ) COCH ₃ found
calc. 45.57
46.10 3.21
2.58 3.17
3.47 8.18
8.75 14.26
14.12 34 Z Cl H OCONHCH ₃ 85-88 found
calc. 49.50
49.40 3.14
3.12 8.02
7.18 9.48
9.08 14.76
14.60 CO Cl H NHCOC ₂ H ₅ oil
* 7.01
7.20 9.12
9.12 14.71
14.68 O)
GJ boiling point OO ■

del X
•
egg y
H I. Z
NHCOCH ₂ Cl Table II (Continuation) 44.51
44.03 1.85
2.22 6.60
6.85 17.34
17.33 14.90
13.93 VkI Ex Z Cl H CH ₃ mFp. ( ⁰ C) found
calc. 50.91
50.70 2.81
2.73 4.31
4.22 10.63
10.69 16.95
17.19 -P-
I. No. Z Cl H "λ /
OCH ₂ CHCH ₂ oil found
calc. 44.15
44.34 1.58
1.72 4.09
3.98 18.13
20.14 18.48
16.19 35 Z Cl H OCh ₂ CHOHCH ₂ OH * 135 ° C /
0.08 mm found
calc. 47.88
49.30 2.50
2.84 3.32
3.60 10.58
9.11 14.82
Iw, 63 36 Z Cl H OCH ₂ CH ₂ SCH ₃
• ι * 153 ° C /
0.24 mm found
calc. 47.49
49.00 3.32
3.35 3.35
3.58 8.88
9.05 14.73
14.58 37 Z Cl H ⁷ N (C ₃ H ₇ -Ii) ₂ 49-53 found
calc. 47.09
47.12 2.95
3.21 3.34
3.44 8.80
8.69 14.05
13.98 38 Z Cl H OCH ₂ CH ₂ SO ₂ CH ₃ 59-64 found
calc. 54.04
54.75 4.62
4.84 6.34
6.72 8.71
8.50 13.55
13.67 39 Z Cl H N (CH ₃ ) CH ₂ GH ₂ OH
NHCONHCH ₃ 42-45 found
calc. 43.53
43.69 2.71
2.98 2.99
3.19 8.27
8.06 13.19
12.96 40 Z Cl
Cl H
. H. NHCOSC ₂ H ₅ oil , 5 found.
calc. 48.95
49.18
46.52
46.22 3.65
3.61
2.56
2.85 7.18
7.17
10.76
10.78 9.29
9.07
9.40
9.10 14.87
14.59
IS>
14.47 <■ *>
14.63 -J 41 Z
Z Cl H 127.5-129 found
calc.
found
calc. 45.76
45.66 2.88
2.88 6.77
6.66 8.58
8.42 13.24 CD
13.55 id 42 Z [Oil
204-208 found
calc. 43
44 111-112 45

boiling point

Example XY No. -

CD CO CO

46 Z

47 Z

48 Z

49 Z

50 t

51 Z

52 Z

53 Z

54 Z

55 Z

56 Z

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

Cl H

CN

COgH

CO ₂ CH ₃

Table II (continued) mFp. ( ⁰ C)

J) ₂ '99-100 95-103 140-150

oil

OCH (CH ₃ ) COgCH ₃ 68-70 OCH (CH ₃ ) CONHg 108-111 OCH (CH ₃ ) CONHCh ₃ 121-126 OCH (CH ₃ ) CON (CH ₃ ) g 83-85 N (CgH ₅ ) CH ₂ CHgOH N (C ₂ H ₅ ) CONHCH ₃ 127.5-128.5

OC ₂ H ₅

100.5-102

found
calc. 45.08
44.84 3.14
3.17 5.53
5.50 7.20
6.97 11.03
11.20 cn
co
GO I.
Oil found
calc. 49.92
49.05 1.82
1.77 7.68
8.18 11.57
10.35 15.69
16.65 VJi
I. found
calc. 46.26
46.50 1.86
1.95 / 3.45
3.87 11.03
9.82 14.48
15.78 found
calc. 47.77
47.90 2.64
2.42 3.48
3.73 10.49
9.45 12.93
15.20 found
calc. 48.58
48.60 2.98
2.98
j 3.15
3.35 8.58
8.43 13.73
13.58 found
calc. 47.61
47,, 5O 3.21
2.99 6.70
6.93 8.98
8.78 14.37
14.10 found
calc. 48 ⁷ , 68
48.80 3.53
3.37 6.54
6.70 8.78
8.48 13.72
13.62 found
calc. 50.17
50.00 3.78
3.73 6.25
6.48 8.37
8.20 13.22
13.18 found
calc. 50.44
50.27 3.99.
4.10 6.92
6.89 8.76
8.86 14.08
14.18 found
calc. 49.51
48.87 3.91
3.62 9.95
10.06 8.64
8.49 12.60
13.64 found
calc. 45.26
45.47 2.43
2.54 3.36
3.54 18.00
17.90 12.33
14.39

Example 3 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3-ethoxy-4-nitrophenyl ether . __

Procedure A

a) 1,3-bis (2-chloro-alpha, alpha, alpha-trifluoro-p-tolyloxy) benzene A solution of potassium hydroxide (3.26 g; 0.05 mol; 85%) in water (about 3 g) is slowly and dropwise into a solution of resorcinol (2.75 g; 0.025 mol) and 3,4-dichloro-alpha, alpha, alpha-trifluorotoluene (10.75 g; 0.05 mol) in tetramethylene sulfone (125 al) given at 150-160 ° C with stirring. After the addition is complete, the strongly colored reaction mixture is

"Schung stirred overnight at 150 - 160 ° C, with benzene (200 ml) diluted and carefully washed with water (700 ml). Hexane (200 ml) is then added and the mixture is washed with Washed water (600 ml), then with dilute sulfuric acid (600 ml), dilute sodium hydroxide solution (600 ml) and water (600 ml). The solution is then dried and the solvent removed, 1,3-bis (2-chloro-alpha, alpha, alpha, trifluoro-p-tolyloxy) benzene (8.6 g; 65%) with a boiling point from 160 - 170 ° C / 0.1 mm.

b) 1,3-bis (2-chloro-alpha, alpha, alpha-trifluoro-p-tolyloxy) -4 -nitrobenzene

1,3-bis (2-chloro-alpha, alpha, alpha-trifluoro-p-tolyloxy) benzene (12 g; 0.0255 mol) is added to a mixture of concentrated nitric acid (12 g) and concentrated sulfuric acid (15 g) given at 5 ° C. Then the temperature is allowed with stirring by hand and slight cooling with an ice bath to 25 - 30 ⁰ G rise. The oil solidifies after 10 to 20 minutes. The mixture is then taken in water / benzene (400 ml) / hexane (400 ml) and the organic phase is washed with water, dried, filtered through activated silica gel (about 20 g) and the solvents are removed. The residue is recrystallized from isopropanol, 1,3-bis (2-chloro-

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alpha, alpha, alpha-trifluoro-p-tolyloxy) -4-nitrobenzene (7.4 g; 5696) with a melting point of 110-111.5 ° C.

c) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-

4-nitrophenyl ether

A 10 # solution of potassium hydroxide in ethanol (10 ml) becomes a solution of 1,3-bis (2-chloro-alpha, alpha, alphatrifluoro-p-tolyloxy) -4-nitrobenzene (2 g; 0.0039 mol) in dioxane (20 ml). After the solution has been at for 40 minutes Having been held at room temperature, it is warmed to 45 ° C for 8 minutes; then it is cooled with benzene (50 ml) and hexane (50 ml) and washed with water (3 x 100 ml), dried and the solvents are removed. The residue is recrystallized from isopropanol, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (1.21 g; 8696) melting point 83-84 ° C receives.

Procedure B

a) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-hydroxy-

phenvlether

A mixture of the di-potassium salt of resorcinol (186.3 g; 1 mole), 3,4-dichloro-alpha, alpha, alpha-trifluorotoluene (53.7 g; 0.25 mol) and tetramethylene sulfone (100 ml) Stirred at 140 ° -16O ° C. for 30 hours.

Benzene (500 ml) and water (200 ml) are then added, and the organic phase is washed with water (3 x 200 ml), diluted with hexane (500 ml) and again with water washed, dried, over activated silica gel (15 g) filtered, the solvent removed and the residue distilled, 2-chloro-alpha, alpha, alpha-trifluorop-tolyl-3-hydroxyphenyl ether (45.1 g; 62Ji) with a boiling point of 112-124 ° C / 0.3 mm.

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b) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy phenyl ether

A mixture of 2-chloro-alpha, alpha, alpha-trifluoro-ptolyl-3-hydroxyphenyl ether (184 g) and acetic anhydride (334 g) is heated on a steam bath for one hour and then chilled. The mixture is washed with 5% sodium carbonate solution (2 × 500 ml) and then distilled, whereby one 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxyphenyl ether (84 g; 40%) with a boiling point of 107-117 ° C / 0.09 mm.

c) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy-4-

nitrophenyl ether _________________

A solution of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxyphenyl ether (249 g; 0.75 mol) in 1,2-dichloroethane (1200 ml) is 2.2 hours at 20 - 30 ° C with a mixture of concentrated sulfuric acid (276 g) and nitric acid, 70% (227 g) stirred. Hexane (700 ml) is added and the oil layer is washed once with water, three times with dilute sodium bicarbonate solution and again with water. Then it is dried over activated silica gel (about 40 g) filtered and the solvents removed. The product is crystallized from hexane-benzene, whereby one 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy-4-nitrophenyl ether (207.5 g; 73%) with a melting point of 83-89 ° C.

d) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-hydroxy- 4-nitrophenyl ether

A solution of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy-4-nitrophenyl ether (204.9 g; 0.545 mol) in methanol (2900 ml) is treated with potassium carbonate for one hour at 20 ° C (103 g; 0.745 mol) stirred. 90% of the methanol is removed and there is benzene (1 liter), 7-8% sulfuric acid solution (1600 ml) were added and the mixture was stirred at 25 ° C. for 1.5 hours. The oil layer is washed twice with water (each time

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200 ml) washed, dried, over activated silica gel (40 g) filtered, the solvents are removed, and. the residue is crystallized from hexane, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-hydroxy-4-nitrophenyl ether (165.3 g; 90%) of melting point 68.5 73 ° C is obtained.

e) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-

4-nitrophenyl ether

A solution of 2-chloro-alpha, alpha, alpha-trifluoro-p-trifluoro-p-tolyl-3-hydroxy-4-nitrophenyl ether (60 g; 0.018 mole; 73% pure) and dimethylformamide (100 g) is added to the potassium phenoxide converted and stirred with ethyl bromide (35 g; 0.32 mol) for 3 hours at 60 ° C and 5 hours at 80 ° C. It Perchlorethylene (150 g) is added and the solution is washed twice with water (about 250 ml each time) at 50 ° C. The solvents are removed and 2-chloralpha is obtained , alpha, alpha-trifluoro-p-tolyl-S-ethoxy ^ -nitrophenyl ether (56 g; 83%, 71% pure) Λ

Example 7 Z "~ ^:

Production of 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl- 3-ethoxy-4-nitrophenyl ether

A solution of potassium hydroxide (2.6 g; 0.04 mole; 87.3% pure) and 3-ethoxy-4-nitrophenol (7.3 g; 0.04 mol) in methanol (30 ml) is evaporated to dryness under reduced pressure. The resulting residue of potassium 3-ethoxy-4-nitrophenoxide is dissolved in tetramethylene sulfone (200 g) and 4-chloro-3-cyano-benzotrifluoride (8.2 g; 0.04 mol) is added. Gas-liquid chromatography indicates the reaction is complete after 4 1/2 hours at 110 ° C and 2 1/2 hours at 135 ° C has been stirred. The reaction mixture is cooled and poured into deionized water poured, and the resulting precipitate is filtered off and air dried. After recrystallization in

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Isopropanol gives 2-cyano-alpha, alpha, alpha-trifluorop-tolyl-3-ethoxy-4-nitrophenyl ether (7.4 g; 53%) with a melting point of 143-145 ° C.

Example 19 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-

3-ethylamino-4-nitrophenyl ether

A solution of 1,3-bis (S-chloro-alpha, alpha, alpha-trifluorop-tolyloxy) -4-nitrobenzene (12.8 g; 0.025 mol) and ethylamine (6.7 g; 0.15 mol) in dioxane (120 ml) is placed in a pressure bottle 4.5 hours at 50 - 55 ° C and 4.3 hours at 90 95 ° C heated. Benzene (200 ml), hexane (70 ml) and water (500 ml) are added and the organic phase is mixed with Water (500 ml), 10% sodium bicarbonate solution (200 ml) and water (200 ml), then dried, filtered through activated silica gel (25 g), the solvents become removed, and the residue is crystallized from hexane, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethylamino-4-nitrophenyl ether (7.9 g; 88%) with a melting point of 82-83 ° C is obtained.

Example 21 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3-diethylamino-4-nitroph, enyl ether

A solution of 1,3-bis (2-chloro-alpha, alpha, alpha-trifluorop-tolyloxy) -4-nitrobenzene (12.8 g; 0.025 mol) in p-dioxane (130 "ml) is refluxed for 26 hours at 65 95 ° C heated with diethylamine (50 g; 0.66 mol). There are benzene (about 200 ml) and water (about 500 ml) and then Hexane (about 70 ml) added. The oil layer formed is separated off, first with water (500 ml) and then with 10 ^ iger Sodium bicarbonate solution (200 ml) and then washed again with water (200 ml). After drying it is activated over Filtered silica gel (about 25 g), and remove the solvents

309839/1235

are then removed. The oil remaining as a residue is distilled in vacuo, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-diethylamine-4-nitrophenyl ether (8.15 g; 8496) with a boiling point of 180 - 190 ° C / 0.01 mm.

Example 25 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3- (1-carboxyethoxy) -4- »nitrophenyl ether 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1 -carbethoxyethoxy) -4-nitrophenyl ether (8.6 g; 0.02 mol), 86% potassium hydroxide (2.6 g; 0.04 mol), ethanol (8 ml), dioxane (8 ml) and water (100 ml) are heated to 90 - 95 ° C for 30 minutes. Ether (200 ml) and water (200 ml) are then added, and the mixture is acidified with dilute sulfuric acid, the water layer is extracted three times with ether (200 ml each time), dried, and the ether is removed, taking 2- Chlorine-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carboxyethoxy) -4-nitrophenyl ether (6.4 g; 7996) with a melting point of 108-109 ° C. is obtained.

Example 26 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3- (1-carbäthoxväthoxv) -4-nltrophenvläther potassium-2-nitro-5- (2-chloro-alpha, alpha, alpha-trifluor- p-tolyloxy) phenoxid (7.4 g; 0.02 mol), ethyl 2-bromopropionate (3.6 g; 0.02 mol) and tetramethylene sulfone (50 ml) are adjusted to 90-95 for 1.5 hours ° C heated. Benzene (100 ml) and hexane (100 ml) are added and the solution is washed with a dilute sodium carbonate solution, then with water, dried and the solvents are removed. The residue is crystallized from pentane, using 2-chloralpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carbethoxyethoxy) -4-nitrophenyl ether (6.2 g; 71 #) with a melting point of 71-74 ° C receives.

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Example 37 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3-chloro-4-nitrophenyl ether
a) 3-chloro-4-nitrofluorobenzene

m-Chlorofluorobenzene (240 g; 1.85 mol) becomes a mixture of sulfuric acid (185 g; 1.85 mol) and nitric acid (166 g; 1.85 mol) at -5 ° C in 3.5 hours, stirred for 13 hours, and then benzene (200 ml) and hexane (200 ml) are added. The extract is washed with water (1 χ 300 ml), then with a sodium carbonate solution (Ix 300 ml) and then again with water (l χ 300 ml); then it is dried and the solvents are removed. The residue is distilled, 138 g of a mixture of isomers being obtained. The 4-nitro isomer crystallizes and is filtered off, 3-chloro-4-nitro-fluorobenzene (51 g; 16.7%) being obtained from a Melting point of 36-38 ° C.

Examples 42 Z - 49 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3-carbomethoxy-4-nitrophenyl ether
a) 3-cyano-4-nitrofluorobenzene

m-Fluorobenzonitrile (96.8 g; 0.8 mol) is added to a mixture of concentrated sulfuric acid (600 ml) and potassium nitrate (80.9 g; 0.8 mol) at 3-6 ° C. in 2 1/2 hours given. The mixture is then allowed to warm to 25 ° C. The mixture is then poured over crushed ice (3000 ml), extracted with chloroform (5 x 250 ml), dried and the solvent is removed. The residue is extracted with pentane and dried, 3-cyano-4-nitrofluorobenzene (115 g; 86.5%) having a melting point of 102-104 ° C. being obtained.

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b) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-cyano-4- nitrophenyl ether

The potassium phenoxide produced in tetramethylene sulfone at 5 ° C by 2-chloro-alpha, alpha, alpha-trifluoro-p-cresol (13.5 g; 0.0688 mol) is added to a solution of 3-cyano-4-nitrofluoro benzene (11.4 g; 0.0688 mol) in tetramethylene sulfone 120 ° C given in 4 hours, then stirred for a further 18 hours and then cooled. There are benzene (200 ml) and hexane (100 ml) are added, and the solution is washed with water (5 × 250 ml), dried, filtered, and the solvents being deleted. The residue is crystallized, using 2-chloro-alpha, alpha, alpha-p-tolyl-3-cyano-4-nitrophenyl ether (16.3 g; 69%) with a melting point from 95 - 103 ° C in 85% purity.

c) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-carboxy- 4-nitrophenyl ether

2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-cyano-4-nitrophenyl ether (11.2 g; 0.0327 mol), acetic acid (25 ml) and hydrobromic acid (12 ml; 47, 8%) are heated to 120 ° C in a pressure bottle for 2 days, poured over crushed ice and extracted with benzene (2 × 150 ml). The benzene solution is dried and filtered; then the solvent is removed and the residue is crystallized from pentane, with 2-chloro-alpha, alpha, alpha-trifluoro-p-to IyI-3-carboxy-4-nitrophenyl ether (7.5 g; 63.5 %) with a Melting point of 140-150 ° C is obtained in a purity of 85%. '

d) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-carbo methoxy-4-nitrophenyl ether

With a solution of 2-chloro-alpha, alpha, alpha-trifluorop-tolyl-3-carboxy-4-nitrophenyl ether (2.3 g; 0.0064 mol) in methanol (50 ml) is hydrogen chloride for 10 hours passed at 32 ° C; the solution is stirred overnight and

309839/1235

the solvent is removed, with 2-chloro-alpha, alpha, alpha-trif luor-p-tolyl ^ -carbomethoxy ^ -nitrophenyl ether (1.5 g; 40%) is obtained.

Example 51 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3- (1-carbamoylethoxy) -4-nitrophenyl ether

a) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (l- chloroformylethoxy) -4-nitrophenyl ether

2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carboxyethoxy) -4-nitrophenyl ether (34.8 g; 0.086 mol), thionyl chloride (20.4 g; 0.172 mol) and benzene (150 ml) are 5 Stirred at 95 ° C. for 16 hours and at 25 ° C. for 16 hours. The benzene is removed and 2-chloro-alpha, alpha, alphatrif is obtained luoro-p-tolyl-3- (1-chloroformylethoxy) -4-nitrophenyl ether (33.4 g; 92%).

b) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carbamoyl ethoxy) -4-nitrophenyl ether

A solution of 2_-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-chloroformylethoxy) -4-nitrophenyl ether (4.2 g; 0.01 mol) in ether (50 ml) becomes a Ether solution (200 ml), saturated with gaseous ammonia, given at a temperature of 0 ° C. After 30 minutes, water (100 ml) is added and the ether layer is separated off. The aqueous phase is extracted with ether (3 x 200 ml) and the combined extracts are dried and filtered over activated silica gel (about 20 g). After removing the solvent, 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carbamoylethoxy) -4-nitrophenyl ether (2.4 g; 60%) with a melting point of 108-111 is obtained ⁰ C.

309839/1235

Example 55 Z

Production of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl- 3- (3-methyl-1-ethylureido) -4-nitrophenyl ether

a) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (N-ethyl chloroformamido) -4-nitrophenyl ether

A mixture of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethylamino-4-nitrophenyl ether (3.6 g; 0.01 mol), phosgene (18.9 g; 0.19 mol), 2,6-lutidine (2.2 g; 0.02 mol) and benzene (about 130 ml) are heated in a pressure bottle to 90 * -95 ° C for 64 hours. The mixture is cooled, filtered and the solvent removed. 2-chloro-alpha, alpha, alpha-trifluor-p-tolyl-3- (N-ethylchloroformamido) -4-nitrophenyl ether is obtained.

b) 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (3-methyl- 1-ethylureido) -4-nitrophenyl ether

A solution of 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3- (n-ethylchloroformamido) -4-nitrophenyl ether (4.4 g; 0.01 mol), methylamine (3.3 g; 0.11 Mol) and benzene (about 60 ml) are left to stand at 0 ° C for about 25 minutes, then filtered, and then the solvent is removed. Benzene (about 100 ml) and hexane (50 ml) are added, and the solution is washed with water (100 ml) and then with 10 # aqueous sodium carbonate solution (2 × 100 ml), dried, and the product is activated Silica gel (about 25 g) adsorbed. The product is eluted with a mixture of benzene (400 ml) and methanol (40 ml). The solvents are removed and the product is recrystallized, 2-chloro-alpha, alpha, alpha-trifluoro-ptolyl-3- (3-methyl-1-ethylureide) -4-nitrophenyl ether (2.6 g; 62% ) with a melting point of 127.5 - 128.5 ° C.

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Example 56 Z

Production of 2,6-dichloro-alpha, alpha, alpha-trifluor-p tolvl-3-ethoxy-4-nitrophenyl ether

a) 314-dichloro-5-nitro-alpha, alpha, alpha-trifluorotoluene

3,4-dichloro-alpha, alpha, alpha-trifluorotoluene (862 g; 4.0 mol) is stirred into a mixture of concentrated sulfuric acid (4400 g) and concentrated nitric acid (3400 g) given at 35 ° C. The mixture is 70 minutes at 95 ° C stirred and then left to separate. The 01 layer is applied once with water and twice with a 5% Washed sodium carbonate solution, dried and fractionated distilled. 3,4-dichloro-5-nitro-alpha, alpha, alpha-trifluorotoluene (188 g; 18%) with a boiling point of 115 - 118 ° C / 15. mm in. of 88% purity.

b) 5-amino-3,4-dichloro-alpha, alpha _t alpha-trifluorotoluene

500 ml of an ethanolic solution of 3,4-dichloro-5-nitroalpha, alpha, alpha-trifluorotoluene (188 g; 0.72 mol) and platinum oxide (Adam's catalyst) (0.2 g) are at room temperature reduced in a Niederdurckhydrierapparat. 5-Amino-3,4-dichloro-alpha, alpha, alpha-trifluorotoluene is obtained (129.9 g; 78%) with a boiling point of 65 - 70 ° C / l-2 mm.

c) ' 3.4 ₁ 5-trichloro-alpha, alpha, alpha-trifluorotoluene A solution of sodium nitrite (39 g) in water (85 ml) is converted into a solution of 5-amino-3,4- dichloro-alpha, alpha, alpha-trifluorotoluene (117.5 g; 0.51 mol) in 1700 ml of concentrated hydrochloric acid at -6 ° C. The solution is stirred for one hour and then filtered. The filtrate becomes a solution of copper-I chloride (76.5 g) in concentrated hydrochloric acid (500 ml) over the course of 5 minutes at 0 to 8 ° C. The temperature is then increased over the course of 80 minutes to 80 ° C. The The reaction mixture is cooled to 35 ° C. and extracted with hexane (2 × 300 ml). The extract is first mixed with water and

309839/1235

then washed with 2% sodium hydroxide solution, dried and distilled, being 3,4,5-trichloro-alpha, alpha, alphatrifluorotoluene (70 g; 55%) with a boiling point of 82-86 ° C / 10 mm in a purity of 95%.

d) 1,3-bis (2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl oxy) benzene

A mixture of 3,4,5-trichloro-alpha, alpha, alpha-trifluorotoluene (10 g; 0.04 mol) and the dipotassium salt of 1,3-dihydroxybenzene (4 g; 0.021 mol) in 150 ml of tetramethylene sulfone is heated to about 120 ° C. for 70 minutes while stirring. the The cooled reaction mixture is diluted with benzene (350 ml) and washed once with water (100 ml). It becomes hexane (200 ml) are added and the solution is then washed with water (3 x 500 ml), then dried over activated Filter silica gel (about 25 g) and remove the solvents. The remaining oil becomes from a Mixture of pentane and benzene crystallizes, whereby 1,3-bis (2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyloxy) -benzene (5 »3 g; 49%) with a melting point of 121-122 ° C receives.

e) 1,3-bis (2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl oxy) -4-ni tr top oil

A cooled mixture of concentrated sulfuric acid (6.5 ml) and concentrated nitric acid (4.4 ml) is added with stirring to an ice-cold solution of 1,3-bis (2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyloxy) benzene (11.1 g; 0.021 mol) given in 1,2-dichloroethane (30 ml). After 30 minutes at Phase separation is allowed to occur at room temperature and the organic phase is washed twice with water. It benzene (200 ml) is then added and the solution is washed twice with dilute sodium carbonate solution, dried, filtered through activated silica gel (about 25 g) and the solvents removed. The ones left behind Crystals are treated with pentane, filtered and dried

309839/1235

net, being 1,3-bis (2,6-dichloro-alpha, alpha _f alpha-trifluoro-p-tolyloxy) -4-nitrobenzene (9 »9 gj 82%) with a melting point of 137.5-140.5 ° C is obtained in a purity of 90%.

f) 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-

4-nitrophenyl ether

A solution of 86% potassium hydroxide (1.9 g; 0.029 mol) in ethanol (20 ml) is added to a solution of 1,3-bis (2,6-dichloro-alpha, alpha, alpha-trifluoro-p- tolyloxy) -4-nitrobenzene (8.0 g; 0.014 mol) in p-dioxane (70 ml) and the mixture is heated to 50 ° C. for one hour. The solution is cooled and benzene (about 250 ml) is added. Crystals of potassium 2-nitro-5- (2,6-dichloroalpha, alpha, alpha-trifluoro-p-tolyloxy) phenoxide (2.9 g; 52%) separate out and can be separated off. Treatment with acids gives the free phenol, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-hydroxy-4-nitrophenyl ether (2.0 g; 40%) ^x with a melting point of 84 , 5 - 86.5 ° C. This phenol (1.7 g; 0.0046 mol) is converted back into the potassium salt, dissolved in dimethylformamide (20 ml) and treated with ethyl iodide (1.2 g; 0.0077 Mol) treated at 50-70 ° C for 2.5 hours. The reaction mixture is diluted with benzene (about 100 ml) and hexane (about 50 ml), washed with water (3 x 100 ml), dried and filtered through activated silica gel (about 15 g). After removing the solvent, 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (0.8 g; 44%) with a melting point of 100.5-102 is obtained ° C.

The filtrate from the 2.9 g of phenoxide becomes ethyl 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl ether (3.0 g; 82%) with a boiling point of 78 ° C / 5 mm and an additional amount of the product 2,6-dichloro-alpha, alpha, alpha-trifluorop-tolyl-3-ethoxy-4-nitrophenyl ether (0.35 g; 6%) with a melting point of 88-93 ° C.

309839/1235

For example 57 to 72

Other diphenyl ethers of the formula I are prepared according to the procedure of Examples 1 to 56 Z. The compounds made in this way include the following substances:
alpha, alpha, aljpha, alpha, alpha ', alpha -Hexaf luor-2,4-xyIyI-

3-ethoxy-4-nitrophenyl ether,
alpha, alpha, alpha -trifluoro-2,4-xylyl-3-n-propoxy-4-nitro-

phenyl ether,
2-chloro-6, alpha, alpha, alpha-tetrafluoro-p-tolyl-3-ethyl-4-

nitrophenyl ether,
2-iodine-alpha, alpha, alpha-trifluoro-p-tolyl-3-methoxy-4-nitro-

phenyl ether,
2-chloro-6-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3-methyl-

thio-4-riitrophenyl ether,
2-bromo-alpha, alpha, alpha -trifluoro-4,6-xylyl-3ratshoxy-4-

nitrophenyl ether,
2-chloro-alpha, alpha, alpha, alpha ', alpha *, alpha'-hexafluoro-

. 4,6-xylyl-3-methoxy-4-nitrophenyl ether, "· 2-bromo-alpha, alpha, alpha-trifluoro-p-tolyl-S-ethoxy ^ -nitro-

phenyl ether,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-n-butyl-4-

nitrophenyl ether,
2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-bromo-4-nitro-

phenyl ether,
2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3-acetoxy-4-nitrο

phenyl ether,
2-Brpm-alpha, alpha, alpha-trifluoro-p-tolyl-3-diethylamino-

4-nitrophenyl ether,
. 2,6-dichloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethylamino-

4-nitrophenyl ether,
^: 2-cyano-alpha, alpha, alpha-trifluoro-p-tolyl-3- (1-carbethoxy-

ethoxy) -4-nitrophenyl ether,
2-cyano-alpha, alpha _f alpha-trifluoro-p-tolyl-3-carbomethoxy-

4-nitrophenyl ether,

309839/1235

2-Brpm-alpha, alpha, alpha-trifluoro-p-tolyl-3-carboxy-4-

nitrophenyl ether.
These diphenyl ethers have herbicidal properties.

With regard to the nomenclature, the statement made earlier that the nomenclature the "Chemical Abstract" was used, but the. Connections according to the invention also correct in other ways are designated.

The following examples illustrate the herbicidal properties shown the diphenyl ether according to the invention.

Example 73

This example shows the herbicidal activity of the diphenyl ethers according to the invention against a number of common weeds. Using the procedure described later, the diphenyl ethers were used to control the following "weeds" for effectiveness: At 1.12 kg / 1000 m (10 pounds per acre);

Mojiocotyledons dicotyledons

Echinochloa crus. Convolvulus arvensis

Digitaria spp. Rumex crispus

Cyperus esculentus Abutilon theophrasti

Avena fatua Brassica haber

At 0.224 and 0.448 kg / 1000 m (2 and 4 pounds per acre)

Monocots dicots

Echinochloa crusgalll Convolvulus arvensis

** Cynodon dactylon Xanthium pensylvanicum

Digitaria spp. ** Sesbania macrocarpa

Bromus tectorum ^{+ Rumex C} ^ ^S P ^US

Setaria faberii . 'Chenopodium album

309839/1235

Monocots dicots

Sorghum halepense Iopmoea purpurea Cyperus esculentus * Amaranthus retroflexus

Agropyron repens. ** Ambrosia artemisiifolia

* Lolium perenne * Polygonum pensylvanicum

* Avena fatua ** Lycopersicon esculentum

* Panicum miliaceum Abutilon theophrasti

* Daucus carota

* Brassica haber

* Examples 1 to 5 only
** Examples 6 to 8 only

The following test procedure is used. Seeds from selected crops and weeds are planted in the ground in shallow trays. For the tests before the plants become visible, the flat dishes are treated with the test compound immediately after planting. For tests after the plants have become visible, the plants are allowed to germinate, and the flat dishes are treated with the compound to be tested after two weeks. The compound to be tested is dissolved in acetone, the solution is diluted with water and sprayed over the flat dishes, using a carrier volume of 47 liters / 1000 m (50 gallons per acre) at the dosage indicated in the tables. About two weeks after the addition of the compound to be tested, the growth status of the plant is observed and the phytotoxic effect of the compound is assessed. Table III shows the mean percentage of the control which is achieved by the test compound, the plants being destroyed by the compound being given as a percentage.

309839/1235

Table « (% Control) 0.448 0.224 After this
Becoming visible 0.448 0, , 22 3 III 82 71 1.12 75 74 Herbicide effective wedge 52 51 99 74 81 Connect
dung of 96 96 100 99 92 example
No. Before the
Becoming visible 100 88 100 92 85 1 kg / 1000 m ² 1.12 96 100 87 M * 96 71 100 77 2 D * 97 99 100 94 M. 77 83 100 94 3 D. 97 73 100 19th M. 94 39 77 49 4th D. 95. 100 90 86 M. 87 100 99 5 D. 100 86 75 34 46 M. 0 85 73 73 92 6th 0 81 72 24 35 ■ M 82 78 70 73 7th M. 8th D. M. D.

* M = monocolytes; D = dicolytes

Example 74

This example shows the selective herbicidal activity of * diphehyl ethers according to the invention in a variety of agricultural applications Cultures. Using the test procedure of Example 73, the tolerance of the diphenyl ethers is determined according to the Invention tested against the following common agricultural crops, but not all compounds are

309839/1235

GenUber each culture to be examined: alfalfa, beans (snapbeans), corn, cotton, cucumber, peanuts, rapeseed, rice, soybeans ,. Tomatoes and wheat. Of a significant tolerance is spoken if 5096 or less of the tested Crops killed at a certain dosage that are more than 5096 of many or all weeds of example 73 kills.

The tolerance to beans (snapbeans) when used before the plants are visible are shown by the compounds of Examples 1, 2 and 6. Tolerances to corn when used before the plants are visible are shown by the compounds of Examples 1 and 2 and when used after the plants are visible of Examples 1, 2 and 6. Tolerance to cotton in the applications before it becomes visible is shown by the compounds of Examples 1, 2 and 6 and in applications after it has become visible or laid on (layby applications) the compound of Example 1. Opposite peanuts in applications before the compounds of Examples 1 and 2 become visible, tolerance. Tolerance to soybeans is shown by the compounds of Examples 1 and 2 in pre-visibility applications and the compound of Example 2 after exposure or application. Rice tolerance is shown by the compounds of Examples 1 and 2 in pre-exposure applications and post-exposure applications or after the rice plants have been transplanted, the compounds of Examples 1, 2 and 8. The compounds of Examples 1, 2 and 6 show tolerance to wheat when used both before they have become visible and after they have become visible.

Example 75

This example shows the herbicidal effectiveness of diphenyl ether according to the invention against a number of weeds. Using the method characterized later the diphenyl ethers are effective in the following

Weeds checked:

309839/1235

At 1.12 kg / 1000 m ² (10 pounds per acre):

Monocots

Echinochloa crusgalli Digitaria spp. Cyperus esculentus Avena fatua

Dicots

Convolvulus arvensis Rumex crispus Abbutilon theophrasti Brassica haber

At 0.224 and 0.448 kg / 1000 m (2 and 4 pounds per acre):

Monocots

Echinochloa crusgalli Cynodon dactylon ** Digitaria spp. Bromus tectorum * Setaria faberii Sorghum haiepensβ Cyperus esculentus Agropyron repens LoIium perenne * Avena fatua * Panicum miliaceum *

Dicots

Convolvulus arvensis Xanthium pensylvanicum Sesbania macrocarpa ** Rumex crispus * Chenopodium album * Ipomoea purpurea Amaranthus retroflexus * Ambrosia artemisiifolia ** Polygonum pensylvanlcum *

309839/1235

Lycopersicon esculentum ** Abutilon theophrasti Daucus carota *.

BrassAca haber * -c -

* Only examples 1 Z to 9 Z ** Only examples 10 Z to 56 Z

The following test method was used: Seeds of crops and weeds were planted in the ground in shallow trays. For tests before becoming visible of the plants, the soil in the shallow dishes was treated with the test compound immediately after planting. For post-plant visibility tests, the seeds were germinated and after 2 weeks the flat pan was treated with the test compound. The connection under test becomes dissolved in acetone, diluted with water and sprayed over the flat pans. A carrier volume was used that 47 liters / 1000 m (50 gallons per acre) is equivalent; the dosage used (kg / m) is given in the tables. About 2 weeks after application of the test compound, the state of growth of the plants was observed, and the phytotoxic one Effect of the connection was evaluated. Table IV shows the percentage mean values for plant control that was achieved with the test compounds. The percentages indicate which part of the plants by the Connections were destroyed.

WlOOOm ² 3 Table IV • After this 2 0.448 0.224 M * Herbicidal effect Becoming visible 57 D * (% Control) 1.1; 58 Connect M. 82 99 dung of D. Before the 100 100 example Becoming visible 100 No. 1.12 0.448 0.224 100 1 line 42 76 .35 45 2 Z 97 97 100 80 09839 / 123B

Table IV Z M.
D. (Continuation) • 0.448 0.224 231 1638 99
100 +96
+97 Z M.
D. Before the
Becoming visible ■ 89
99 ** 84
** 66 I.
After this
Becoming visible 80
100 Connect
dung of Example ₅
No. Kg / 1000 πΓ Z M.
D. 1.12 98
100 1.12 0.448 0.224 99
IO9 3 Z M.
D. 99
100 84
78 100
100 91
94 4th Z M.
D. 77
55 75
77 CM O
CO CO 5 Z M.
D. 97
100 65
57 65-
54 100
100 48
80 35
66 6th Z M-
D. 65
70 . 61
57 52
46 97
100 97
81 82
75 7th Z M.
D. '61
60 90
66 81
67 100
100 67
98 17th 8th Z M.
D. 81
82 70
100 66
70 85
100 82
99 100
100 9 Z M.
D. . 99
92 81
98 88
99 100
100 77
100 99
100 IO Z M.
D. 86
96 72
93 77
98 100
100 11 Z M.
D. 76
90 78
72 61
94 91
100 12th 15 Z
** 56 (^ / 1000 ι
+ 28 | i (g / 1000] M.
D.
m ² 64
78 30th
22nd 79
99 76
94 13th 99
100 68
90 14th

30 9 8 39/1235

Table IV (continued)

Connect
dung of lte / 1000 m ² Before the
Becoming visible 0.224 After this
Becoming visible 0.224 example
No. M. 0.446 67 0.448 82 16 Z D. 86 75 77 94 M. 94 20th 96 39 17 Z D. 51 31 45 98 • M. 84 99 89 28 18 Z D. 67 100 28 98 • M. 100 77 86 94 19 Z D. 91 91 84 97 ; M. 96 80 98 80 20 Z D. 88 93 78 97 M. 99 79 88 90 21 Z P. 91 90 74 94 M. 99 63 96 70 22 Z D. 72 77 60 100 M. 98 55 99 71 23 Z D. 90 87 82 100 M. 64 62 100 84 24 Z D. 91 97 86 100 M. 68 40 99 88 25 Z D. 87 93 97 100 ■ M. 88 75 100 93 26 Z D. 98 99 99 100 . M. 100 74 100 99 27 Z D. 76 90 82 100 M. 98 79 100 73 28 Z D. 74 79 73 100 M. 95 66 99 97 29 Z D. 74 84 79 100 73 100

309839/1236

Table IV (continued)

2311639

Connect
dung of Uff / 1000 m ² Before the
Becoming visible 0.224 After this
Becoming visible 0.224 example
No. M. 0.448 78 0.448 91 30 Z D. 81 94 75 100 M. 99 68 100 68 31 Z D. 74 69 61 100 M. 99 81 100 100 32 Z D. 86 81 86 . 100 M. 100 79 100 65 33 Z D. 53 74 32 100 M. '■ 99 83 98 47 34 Z D. 35 85 32 90 M. 52 60 89 63 35 Z D. 40 72 45 80 m ' 40 100 98 94 36 Z D. 93 100 87 98 M. 100 100 100 100 37 Z D. 99 100 92 100 M. 100 62 100 51 38 Z D. 47 68 43 58 M. 86 77 98 61 39 Z D. 65 80 64 100 M. 99 88 98 81 40 Z D. 86 98 64 100 M. 92 84 100 56 41 Z D. 60 62 71 94 • M. 96 83 95 63 42 Z D. 62 60 38 88 ■ M 80 99 98 61 43 Z D. 0 100 2 80 48 47

309839/1236

Table IV (continued)

Connect
dung of M.
D. Before the
Becoming visible Dicots 0.224 • After this
Becoming visible 0.224 M.
D. 0.448 0
17th 100
100 0.448 7th
10 Example _o
No. U £ / 1000 TtC M.
D. 66
96 68
77 VD ON
CO O 53
78 44 Z M.
D. VJl H
OD VX 34
87 17th
88 0
4th 45 Z M.
D. 0
20th 80
80 0
30th 24
84 . 46 Z M.
D. 61
40 100
100 11
72 84
97 47 Z M.
D. 99
97 100
100 75
100 77
100 48 Z M.
D. 92
95 98
100 86
100 100
100 49 Z M.
D. 90
83 96
100 97
100 VO 00
00 ON 50 t M. 79
100 98
75 75
100 93
100 51 Z M.
D. 79
67 98
100 87
100 81
100 52 Z M.
D. 98
83 98
98 79
1.00 71
100 53 Z M.
D. 83
75 79
100 31
96 54 Z * M = monocots; D = 91
73 VO ON
VJl VO 100
99 55 Z 91
83 99
100 56 Z

309839/1235

Example 76

This example demonstrates the selective herbicidal activity of the diphenyl ethers of the invention in a number of agricultural areas Cultivated Plants ». Following the general test method of Example 75, diphenyl ethers were found to be significant Tested tolerance to the following common agricultural crops: alfalfa, beans (snapbeans), corn, cotton, cucumber, peanuts, rapeseed, rice, saffron, soybeans, tomatoes and wheat. It wasn't all compounds examined against all crops. Significant tolerance was understood to mean that 50 - 6 or fewer of the tested crops were destroyed at dosages at which more than 50% of many or all Weeds of Example 75 were destroyed.

The compounds 4Z and 26Z show a tolerance to beans (snapbeans) when applied before the plants become visible. The compounds of Examples 4Z, 11Z, 19Z, 21Z show a tolerance to maize when applied before the plants become visible , 34 Z, 40 Z, 52 Z and 54 Z and, when used, compounds of Examples 4 Z, 18 Z, 19 Z, 21 Z, 26 Z, 34 Z, 36 Z, 40 Z, 49 Z, 52 Z,

53 Z, 54 Z and 56 Z. Compared to cotton, the compounds ^% of Examples 3 Z, 4 Z and 30 Z show a tolerance when used before it becomes visible and the compound of the when used after becoming visible or the "layby" application - Example 3 Z. The compounds of Examples 3 Z, 19 Z, 21 Z, 30 Z, 34 Z, 36 Z, 40 Z, 48 Z, 49 Z, 50 Z, have a tolerance to peanuts when used 52 Z, 53 Z and 56 Z and, when used after they have become visible, the compounds of Examples 4 Z, 18 Z, 34 Z, 36 Z, 37 Z, 40 Z, 48 Z, 53 Z and

54 Z. The compounds of the examples show a tolerance to rice in the applications before it becomes visible 4 T, 19 T, 21 T, 30 T, 34 T, 40 T, 52 T and 54 T and at Use after it has become visible or when it has been replanted

309839/1235

Reis the compounds of Examples 3 Z, 11 Z, 18 Z, 20 Z, 30 Z, 34 Z, 40 Z, 48 Z, 53 Z and 54 Z. The compound of Example 3 Z shows a tolerance to saffron in applications before it becomes visible The compounds of Examples 3 Z, 4 Z, 11 Z, 18 Z, 19 Z, 21 Z, 26 Z, 30 Z, 34 Z, 40 Z, 48 Z, 49 Z, have a tolerance to soybeans in applications before they become visible. 50 Z, 52 Z, 53 Z and 54 Z "and in applications after becoming visible or in the" layby "application, the compounds of Examples 3 Z and 34 Z. The compounds of FIG Examples 4 Z, 18 Z, 19 Z, 26 Z, 34 Z, 40 Z, 50 Z, 54 Z and 56 Z and, for applications after they have become visible, the compounds of Examples 4 Z, 18 Z, 21 Z, 30 Z, 34 Z ₁ 36 Z, 48 Z and 54 Z.

309839/1236

Claims (1)

Patent claims : in which X is a hydrogen atom, a halogen atom, a trihalomethyl radical, a (C, -C <) alkyl radical or a cyano group is; Y is a hydrogen atom, a halogen atom or a trihalo- is methyl radical and • Z is hydrogen, a hydroxyl group, an alkoxy group, an alkyl radical, a halogen atom, an amino group, an alkylthio group, a cyano group, a carboxy group, a carbalkoxy group, a carboxyalkyl group, a • Carbalkoxyalkyl group, an alkanoyloxy group or a Is carbamoyloxy group. 2. A compound according to claim 1, characterized in that Z is an alkyl radical, alkylthio group, carbalkoxy group, Is carboxyalkyl group or alkanoyloxy group, each this contains radicals or groups of up to 4 carbon atoms, or an alkoxy group, or alkoxyalkyl group Carbamoyloxy group with up to 6 carbon atoms in each of these groups. 3. Compound according to claim 1 or 2, characterized in that Y is a hydrogen atom. 309839/1235 4. A compound according to any one of claims 1 to 3, characterized in that that X is a halogen atom or a cyano group. ·. . 5. A compound according to any one of claims 1 to 4, characterized in that that Z is an ethoxy group and X is a cyano group. 6. A compound according to any one of claims 1 to 5 »characterized in that that X is a chlorine atom. 7. A compound according to any one of claims 1 to 6, characterized in that that Z is an alkoxy group. 8. A compound according to claim 7, characterized in that .Z is a non-substituted (C ₁ -C ^) alkoxy group. 9. A compound according to claim 8, characterized in that Z is an ethoxy group and X is a chlorine atom. 10. A compound according to claim 7, characterized in that Z is a halo, hydroxy, alkoxy, carboxy, carbalkoxy, trihalomethyl, alkenyl, alkynyl, amino, alkylamino, dialkylamino, alkylthio, alkylsulfonyl, epoxy, alkylcarbonyl or, is carbamoyl substituted alkoxy group. 11. A compound according to claim 10, characterized in that Z is a carbalkoxy substituted alkoxy group. 12. A compound according to claim 4, characterized in that Z is an amino group. 13. A compound according to claim 12, characterized in that Z is a (C ₁ -C ^) alkyl, 'di (C ₁ -C ^) alkyl, carboxy, carb- (C, -C ^) alkoxy or (C, -Cλ) carbamoyl substituted amino group. 309839/1235 14. A compound according to claim 13, characterized in that Z is a diethylamino group. 15. A compound according to claim 1, characterized in that Y is a halogen atom and X "is a halogen atom, a trifluoromethyl radical, is a (C 1 -C 4) alkyl radical or a cyano group. 16. ' Connection according to claim 1, characterized in that Y and Z are both hydrogen. 17. A compound according to claim 16, characterized in that X is a halogen atom. 18. A compound according to claim 17, characterized in that X is a chlorine atom. 19. A compound according to claim 16, characterized in that X is a cyano group. 20. A compound according to claim 16, characterized in that X 'is a methyl radical. 21. A compound according to claim 1, characterized in that • Y is a halogen atom and X is a halogen atom, a trifluoromethyl radical, is a (C -, - C ^) alkyl radical or a cyano group. 309839/1235 22. Herbicidal agent, characterized in that it is one of the compounds according to one of the preceding as active ingredient Contains claims and an agriculturally useful carrier. 23. Composition according to claim 22, characterized in that the carrier is an inert organic solvent. 24. Composition according to one of claims 22 or 23, characterized ge _r indicates that it contains a surface active agent. 25. Use of one of the agents of claims 22 to 24 for controlling the growth of weeds. 26. methods of controlling the growth of weeds; characterized in that one is on the surface of the A compound according to any one of claims 1 to 21 in one for growth medium prior to the weed becoming visible sufficient to control the growth of weeds Amount applies. 27. The method according to claim 26, characterized in that the compound in an amount of about 11 to about 1345 g / 1000 m is applied. 28. A method for controlling the growth of weeds, characterized in that weed seedlings with a of the compounds of claims 1 to 21 in a sufficient to control the growth of the seedlings, Treated crowd. •. * ■ ■ 29. The method according to claim 28, characterized in that the compound in an amount from about 11 to about 1345 2
g / 1000 m is applied. 309839/1236 .30. Method for controlling undesired vegetation, characterized in that the area in which the plant growth is to be controlled, with a the plant growth-controlling amount of one of the herbicidal agents according to any one of claims 22 to treated. 31 .. Method for the selective control of weeds. in agricultural crops, thus marked ■ 'net that the growth medium before planting the Culture and before the weeds become visible. Binding according to one of claims 1 to 21 in a sufficient one Amount incorporated to control plant growth. 32. The method according to claim 31, characterized in that the compound in an amount of about 11 to about 1,345 g / 1000 m is applied. 309839/1235